Reaction Mechanisms Photocatalytic process efficiency

The key requirement for a SET step in the photocatalytic process seems to be the surface complexation of the substrate, according to an exponential dependence of the probability of electronic tunneling from the distance between the two redox centers [66]. However, as was pointed out in the preceding section on the key role of back reactions, the presence of a SET mechanism could be a disadvantage from an applicative point of view. If the formed SET intermediate (e.g., a radical cation) strongly adsorbs and/or does not transform irreversibly [e.g., by loss of CO from a carboxylic acid or fast reaction with other species (e.g., superoxide or oxygen)], it can act as a recombination center, lowering the overall photon efficiency of the photocatalytic process. 

Although the case that has been previously conunented consisting in the photocatalytic reduction of CO2 by water is the one that could have potential application for the generation of solar fuels, the high endoergonicity of the process and the complex reaction mechanism determine that the efficiency of the process is currently very far from any possible commercial application. As commented earlier, most of the reports on the photocatalytic reduction of CO2 by water describe the formation of a few pmol g h production rate under solar Ught irradiation. 

As reported by Augugliaro et al. [64] the photocatalysis can be combined with chemical or physical operations. In the first case, when the coupling is with ozonation [65, 66], ultrasonic irradiation, photo-Fenton reaction or electrochemical treatment, which influence the photocatalytic mechanism, an increase of the efficiency of the process is obtained. 

Obtaining insight into charge transfer processes is important in order to improve the photoconversion efficiencies in semiconductor-based nanoassemblies. The principles and mechanism of photocatalytic reactions in advanced oxidation processes can be found in earlier review articles [40-42]. Technological advances in this area have already led to the product development for a variety of day-to-day operations. Commercialization of products such as self-cleaning glass, disinfectant tiles and filters for air purification demonstrate the initial success of nanosystems for environmental applications [43]. 

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